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Tuning the optoelectronic and thermoelectric properties of vacancy-ordered halide

perovskites Cs2Ge(1-x)PtxCl6 (x=0, 0.25, 0.50, 0.75 and 1.00) via substitutional
doping of Pt using first-principles approach

Syed Zuhair Abbas Shah, Shanawer Niaz, Fahim Ahmed, Zeesham Abbas, Amna
Parveen, Shahid M. Ramay
PII: S0254-0584(24)00071-3
DOI: https://doi.org/10.1016/j.matchemphys.2024.128947
Reference: MAC 128947

To appear in: Materials Chemistry and Physics

Received Date: 15 October 2023

Revised Date: 20 November 2023
Accepted Date: 14 January 2024

Please cite this article as: S. Zuhair Abbas Shah, S. Niaz, F. Ahmed, Z. Abbas, A. Parveen,
S.M. Ramay, Tuning the optoelectronic and thermoelectric properties of vacancy-ordered halide
perovskites Cs2Ge(1-x)PtxCl6 (x=0, 0.25, 0.50, 0.75 and 1.00) via substitutional doping of Pt using
first-principles approach, Materials Chemistry and Physics (2024), doi: https://doi.org/10.1016/
j.matchemphys.2024.128947.

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© 2024 Published by Elsevier B.V.

Syed Zuhair Abbas Shah: Methodology, Software, Writing- Original draft, Shanawer Niaz:
Conceptualization, Supervision, Visualization, Reviewing and Editing Fahim Ahmed:
Reviewing, Visualization, Zeesham Abbas: Investigation, Supervision, Amna
Parveen: Investigation, Shahid M Ramay: Editing

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Tuning the Optoelectronic and Thermoelectric Properties of Vacancy-
Ordered Halide Perovskites Cs2Ge(1-x)PtxCl6 (x=0, 0.25, 0.50, 0.75 and 1.00) via
Substitutional Doping of Pt Using First-Principles Approach.

Syed Zuhair Abbas Shah*,1,2,3, Shanawer Niaz2,3, Fahim Ahmed4, Zeesham Abbas5,,Amna
Parveen6 and Shahid M Ramay7

1
Institute of Physics, Gomal University, D.I. Khan, 29050, Pakistan.
2
Department of Physics, Thal University Bhakkar, Bhakkar, 30000, Pakistan.
3
Department of Physics, University of Sargodha, Sargodha, 40100, Pakistan

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4
Department of Physics, Division of Science and Technology, University of Education, Lahore
54000, Pakistan

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5
Department of Nanotechnology and Advanced Materials Engineering, Sejong University, Seoul
05006, Republic of Korea
6
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College of Pharmacy, Gachon University, No. 191,Hambakmeoro, Yeonsu-gu, Incheon 21936,
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Republic of Korea
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7
Physics and Astronomy Department, College of Science, King Saud University P.O. Box 2455,
Riyadh 11451, Saudi Arabia
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*Email: zuhair.abbas@uos.edu.pk
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*Tel: +92-300-7668414
Abstract
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Vacancy-ordered halide perovskites have gained considerable attention from researchers

regarding non-traditional energy harvesting applications like solar cells and thermoelectric
generators. However, in most of the reported cases, band gaps are larger (>3.5eV) consequently
the efficiency of solar cells and thermoelectric generators becomes low. Currently, we studied
non-toxic and stable vacancy-ordered halide perovskites Cs2GeCl6 and tuned its band gap via
substitutional doping of Pt (0, 25, 50, 75, and 100%) using the first-principles approach. The
band gap engineering strategy of Pt doping effectively decreased the band gaps (up to 2.50eV)
hence, the more attractive optical and thermoelectric parameters are obtained for instance; high
absorption coefficients (∼105 cm-1), low reflectivity (∼0.3-10%), high optical conductivity
(∼1015 sec-1), and large figure of merits (∼1). Based on these enhanced optical and
thermoelectric performance parameters, the Pt doping strategy can be taken as an effective
practice to tune the band gap significantly in order to stimulate the performance of future solar
cells and thermoelectric generators.

Keywords: Double Perovskites; Density Functional Theory (DFT); Quantum ESPRESSO;

BoltzTraP, Optoelectronic Properties; Thermoelectric Properties;

1. Introduction:

Depleting natural energy reservoirs is a worldwide concern that demands the exploration of
renewable energy sources [1, 2]. Two main sources of energy include sunlight and wasted heat
from various devices and refineries [3, 4]. It has been estimated that around 60 % of the input

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energy is wasted in the form of heat energy [5, 6].Hence, to overcome these issues we rely on

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thermoelectric (TE) generators and Solar cells [7]. The efficiencies of TE generators and Solar

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cells are dependent on the choice of materials and their intrinsic properties. Perovskite material
with the structure of CaTiO3was first discovered in 1839, which exhibits multifunctional
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characteristics [8].The inorganic halide perovskites have attracted the attention of researchers in
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the past ten years due to their outstanding applications in photovoltaics, photo-catalysis, display
technology, X-rays or ultraviolet detection and sensing, piezoelectricity, microwave
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communication devices, spintronic devices, data storage elements as well as in thermoelectricity

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[9-13]. These diverse domains of applications arise from certain alluring properties of
perovskites, for instance, tunable band gaps, charge carrier generation and mobility, high
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absorption in various energy ranges, high optical conductivity, and large figure of merits [14-
17].However, we are unable to utilize all the advantages of the perovskites as mentioned above
due to poor stability and the presence of toxic elements like lead (Pb) [18]. Several studies have
been conducted to address such issues i.e. the stability and toxicity so that we may be able to
obtain sustainable and non-toxic perovskites on a commercial scale in the future [19-21]. The
non-toxic or weakly toxic elements like Sn, Bi, and Sb were used for the replacement of highly
toxic Pb but their photoluminescence quantum yield (PLQY) is very low and stability is also
questionable in most of the cases [22-24].The perovskites with general formulae AB2+X3 (A is a
monovalent metal cation, B2+ is usually divalent Pb and X is halide anion) attracted fame due to
their efficiency in optoelectronics. However, this class suffered two major challenges as
mentioned above i.e. Pb-toxicity and lack of air stability. These drawbacks limited the usage of
the compounds on a commercial scale for optoelectronic and thermoelectric applications. There
were only a few options to replace toxic Pb in its current structural form [25-29], therefore,
addressing the aforementioned limitations of AB2+X3 class, new classes of perovskites such as
double perovskites (DPs) and vacancy-ordered halide double perovskites (VO-HDPs) emerged
with general formulas A2B1+B'3+X6 and A2B4+X6 respectively. The DPs also known as elapsolite
are formed by splitting every adjacent pair of B2+ into monovalent B1+ and trivalent B3+cations.
Bismuth-based DP Cs2AgBiBr6 has been explored with a band gap in the range of 2.05-2.30eV
with fair chemical air stability [30-32].Antimony-based DP Cs2AgSbBr6 was synthesized and it
was found that it is a direct band gap (~1.64eV) semiconductor with comparatively better optical
performance [33]. Similarly, indium-silver-based DPs Cs2InAgX6 (X=Cl,Br,I) were found very

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suitable for optoelectronic properties with direct band gaps in the visible region [34]. A fairly
stable and non-toxic vanadium-based Cs2NaVCl6 has been reported both experimentally [35] and

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theoretically [36] having a band gap of 2eV (experimental) and 2.9eV (theoretical). Applying the

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doping strategy to tune the band gaps, thallium-doped DPs were studied in which the band gap
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was reduced upto ~0.75eV for Cs2Ag1-a Bi1-bTl xBr6with x=0.075 and a large absorption
coefficient was noted in visible range [37].
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Double perovskites with the composition Rb2AgInX6 (X = Cl, Br, I) has been explored using
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first principal calculations for thermoelectric and optical properties. Modification of band gaps
using halide ions is highlighted in this study [38].
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Because of their stable structures and high Curie temperatures, double perovskite oxides have
been the subject of a significant amount of research for use in optoelectronics and magnetic
applications. In particular, carbon-based materials have been discovered to be an acceptable and
affordable replacement that can reduce the requirement for metal electrodes when developing
stable perovskite solar cells [39, 40]. The nickel substitution was utilized to improve the
structural and dielectric properties of a Mg-Zn based material [41].
The class of VO-HDPs was found to have reasonable air stability e.g. CsSnX3 has serious air
instability because Sn2+ oxidizes to Sn4+ very easily and its PLQY is quite low i.e. ~0.14% [22].
In this structural form A2B4+X6, there were plenty of options available to replace Pb with suitable
non-toxic elements without compromising the optoelectronic and thermoelectric performance. It
is actually an antifluorite structural arrangement in which B-site should be tetravalent to retain
charge neutrality.

The Sn4+was found to be the most appropriate candidate to replace Pb4+ on B4+ site [42-44]. In
another study, it was observed that Cs2SnCl6 is a direct wide band gap material having relatively
low PLQY with photoluminescence of blue color. This is due to the large value of its band gap

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(~3.9eV) [45].Generally, it is observed from the literature that A2B4+X6 are found comparatively

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more stable than AB2+X3 but their efficiency is significantly low [46-48]. Substitutional doping

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is one of the most efficient techniques for band gap tuning and hence, enhances the
optoelectronic and thermoelectric efficiency [49, 50]. By doping of bismuth with Cs2SnCl6, a
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blue photoluminescencewas noted with PLQY 78.9% [51], and a red photoluminescence was
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observed with PLQY 37% in the case of Sb doping [52].

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Considering the analysis presented above, we proposed the band gap engineering of Cs2GeCl6via
substitutional doping with cation Pt4+ in various percentages i.e. 0%, 25%, 50%, 75%, and 100%.
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We realized that this band gap engineering strategy made remarkable changes in the
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optoelectronic and thermoelectric properties of the doped systems compared to un-doped

Cs2GeCl6. It is worth notingthat the increasing of Pt4+ cation content results in large values of
absorption coefficients in the diverse frequency range, high optical conductivity, and conversion
of photoluminescence from blue to orange and low reflection in the visible region. Meanwhile,
the values of the Seebeck coefficient and thermoelectric figure of merit have also an increasing
trend with increasing Pt4+ cation content. Based on the predicted results, we are hopeful that the
promising materials under study will open a new gateway as stable, efficient, reliable, and eco-
friendly candidates in future optoelectronics and thermoelectricity.

2. Computational Details:

This investigation was carried out primarily using plane wave pseudopotential code Quantum
ESPRESSO [53] which is based on Kohn Sham equations of density functional theory (DFT).
We used various exchange-correlation (XC) functionals of generalized gradient approximation
(GGA) like PBE [50], RPBE [51], and BEEF-vdW [56] along with Hubbard-U correction [57]
where needed. A 2×2×2 super cell of Cs2GeCl6 was simulated and Pt atoms were substituted in
the form of various percentages i.e. 25%, 50%, 75%, and 100%. All the structures were relaxed
using variable cell relaxation from Broyden, Fletcher, Goldfarb, and Shanno(BFGS) scheme.
The k-mesh of 12×12×12 in accordance with the Monkhorst-Pack scheme [58] was used whereas
the electron convergence criteria were 1×10-6Ry. The cutoffs for the wave function and particle
density were 80 Ry and 480 Ry respectively. While calculating the band structures, a high
symmetry path (Γ—X—U—K—Γ—L—W—X) was chosen using xcrysden [59]. Complex

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dielectric functions were calculated using epsilon.x module of Quantum ESPRESSO whereas
other related optical parameters like absorption coefficient, refractive index, optical conductivity,

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extinction coefficient, reflectivity, and electron loss function were calculated analytically from

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the real and imaginary parts of the complex dielectric functions. The results of self-consistent
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field calculations were coupled with BoltzTraP [60] code which is based on Boltzmann transport
theory to calculate the thermoelectric properties.
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3. Results and Discussion:

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3.1. Structural Properties:

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The perovskite under study whether un-doped (Cs2GeCl6) or doped with Pt for a percentage of
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25, 50, 75, and 100% possess cubic symmetry with space group 𝐹𝑚3̅𝑚. This fact fairly agrees
with the existing literature [61-64]. The compounds under investigation have general formula
A2BX6 with A-site possessing Wyckoff position 8c, B-site 4a, and X-site 24e. The pictorial
representation of the compounds is shown in Fig.1.
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Fig. 1: Crystal structure of vacancy-ordered perovskite Cs2GeCl6 with various doping

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percentages of Pt.
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All the structures i.e. Cs2Ge(1-x)PtxCl6 with x=0.00, 0.25, 0.50, 0.75, and 1.00 were optimized via
variable cell relaxation using the BFGS scheme. The optimized lattice constants with
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experimental and theoretical references are given in Table 1 and it can be concluded that our
calculations for Cs2Ge(1-x)PtxCl6 with x=0.00and 1.00 fairly agree with available literature while
it is worth mentioning that the Pt-content substitution cases with x=0.25, 0.50, and 0.75 are being
reported for the first time.

The structural stability was assessed from Goldschmidt’s tolerance (τt) and octahedral factor (μo).
Mathematically the factors are given by equations (1) and (2) [65].

𝑟𝐴 +𝑟𝑋
τt= (1)
√2(𝑟𝐵 +𝑟𝑋 )

𝑟𝐵
μo= (2)
𝑟𝑋
Here 𝑟𝐴 , 𝑟𝐵 and 𝑟𝑋 are the radii of cations A, B, and anion X respectively. The estimated values of
τt are 1.04, 1.04, 1.03, 1.02, and 1.01, and values of μo are 0.30, 0.31, 0.32, 0.33, and 0.34 for
Cs2Ge(1-x)PtxCl6 with x=0.00, 0.25, 0.50, 0.75, and 1.00 respectively. The values lie in the range
of stable perovskites i.e. 0.8 <τt< 1.1 and 0.3 <μo< 0.8 [13, 66, 67].

Table 1: Lattice constants (Å) of Cs2Ge(1-x)PtxCl6 along with a comparison with available
experimental/theoretical data in the literature.
Work Method Percentage
x=0.00 x=0.25 x=0.50 x=0.75 x=1.00
Present BEEF-vdW 10.11Å 10.10 Å 10.09 Å 10.05 Å 10.04 Å
RPBE 10.50 Å 10.47 Å 10.43 Å 10.39 Å 10.35 Å

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Theoretical PBE-sol 10.61 Å ------- ------- ------- 10.62 Å
[61] [68]

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Experimental ------- ------- ------- ------- ------- 10.59 Å
[62]

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3.2 Electronic Properties:
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The electronic properties are explored in terms of band structures, DOS, and PDOS for Cs2Ge(1-
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x)PtxCl6 (x=0.00, 0.25, 0.50, 0.75, and 1.00). It is clear from Fig.2 (a-e) that all the compounds
under study are direct band gap semiconductors with valence band maxima and conduction band
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minima at Γ-point. The value of the band gap is 3.02 eV for Cs2Ge(1-x)PtxCl6 with x=0 and this
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value gradually decreased with the increasing percentage of Pt doping. This decreasing trend is
very attractive from the applications point of view as we have discussed in sections 3.3 and 3.4.
The values of band gaps along with available reference values are tabulated in Table 2.

In the present study, we employed various exchange-correlation functionals of GGA along with
Hubbard-U correction due to the presence of d-electrons in Pt to obtain better estimates of band
gaps. The high symmetry path Γ-X-U-K-Γ-L-W-X of the irreducible Brillouin zone is considered
and the Fermi level is adjusted at zero for all compounds for convenience.
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Fig.2: Band Structures of vacancy-ordered perovskite Cs2GeCl6 with various doping percentages
i.e. (a) 0, (b) 25, (c) 50, (d) 75, and (e) 100% of Pt
Table 2: Band Gaps (eV) of Cs2Ge(1-x)PtxCl6 along with a comparison with available
experimental/theoretical data in the literature.
Work Method Percentage
x=0.00 x=0.25 x=0.50 x=0.75 x=1.00
Present RPBE+U 3.02 eV 2.98 eV 2.83 eV 2.62 eV 2.50 eV
Theoretical PBE-sol 3.42 eV ------- ------- ------- 2.71 eV
[61] [68]
Experimental ------- ------- ------- ------- ------- 2.30 eV
[62]

Total DOS, element-wise, and orbital-wise PDOS were calculated to probe the contributions

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from various elements and orbitals in the electronic structure of the compounds, which obviously

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gives further insight into electronic properties. The DOS and PDOS plots are presented in Figs.

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Fig.3: DOS and PDOS of Cs2Ge(1-x)PtxCl6 with x=0.

Fig. 3(a-d) illustrates the total DOS and PDOS of Cs2Ge(1-x)PtxCl6 with x=0. There are two
groups separated by the red dashed line (Fermi level) adjusted at zero. The left side of the line
represents the valence band whereas the right side represents the conduction band. The valence
band is mainly composed of Cs-s, Cs-p, and Cl-p orbitals. The conduction band contains
prominent peaks of Ge-total, Cl-p, and Cl-total. Total DOS has major peaks at -3.78eV, -1.01eV,
and 3.66 eV. Fig. 4(a-e) shows the total DOS and PDOS of Cs2Ge(1-x)PtxCl6 with x=0.25. The
valence band contains visible peaks of Cs-s, Cs-p, Pt-total, and Cl-p orbitals whereas the
conduction band has Ge-total, Pt-total, and Cl-p peaks. The total DOS has peaks at -3.78eV, -
2.78eV, -1.08eV, and 3.12eV. The DOS and PDOS profiles of Cs2Ge(1-x)PtxCl6 with x=0.50 are
presented in Fig. 5(a-e). There are major peaks of Cs-s, Cs-p, Ge-total, Pt-total, Pt-d, and Cl-p
orbitals in the valence band while Ge-total, Pt-total, and Cl-p peaks in the conduction band. The
prominent peaks in total DOS reside on -2.78eV, -1.21eV, -0.25eV, and 3.18eV.

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Fig.4: DOS and PDOS of Cs2Ge(1-x)PtxCl6 with x=0.25.

Similarly, the DOS and PDOS graphs of Cs2Ge(1-x)PtxCl6 with x=0.75 are shown in Fig. 6(a-
e).The Cs-s, Cs-p, Ge-total, Pt-total, and Cl-p orbitals are prominent in the valence band whereas
Ge-total, Pt-total, and Cl-p peaks are present in the conduction band. The evident peaks in total
DOS are present at energy values of -3.85, -2.78eV, -1.21eV, and 3.08eV. Finally, the fully Ge is
fully replaced by Pt i.e. Cs2Ge(1-x)PtxCl6 with x=1.00, and its DOS and PDOS are graphically
shown in Fig. 7(a-e). Again, the Cs-s, Cs-p, Pt-total, and Cl-p orbitals are prominent in the
valence band whereas Pt-total, and Cl-p peaks are dominant in the conduction band. The total
DOS profile has major peaks at energy values -2.84, -1.27, and 3.22 eV.
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Fig.5: DOS and PDOS of Cs2Ge(1-x)PtxCl6 with x=0.50.

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Fig.6: DOS and PDOS of Cs2Ge(1-x)PtxCl6 with x=0.75.

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Fig.7: DOS and PDOS of Cs2Ge(1-x)PtxCl6 with x=1.00.
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3.3 Optical Properties:
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Keeping in view the literature study it was found appropriate to explore the optical
characteristics in detail for pristine Cs2GeCl6 as well as its doped variants with 0, 25, 50, 75, and
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100 percent doping of Pt. The important optical parameters like real and imaginary parts of the
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dielectric function, absorption coefficient, refractive index, optical conductivity, extinction

coefficient, reflectivity, and electron loss function are studied in the energy range 0-12 eV.
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Moreover, the relation of optical properties with electronic properties is focused so that the effect
of band gap tuning via substitutional doping of Pt on optical performance may be analyzed.

The dielectric function ε(ω) is a fundamental entity to inspect the optical behavior of a material.
It comprises on real part ε1(ω) and imaginary part ε2(ω) given by equation (3) [69].

ε(ω) = ε1 (ω) + 𝑖ε2 (ω) (3)

The real part ε1(ω) is the measure of a material’s capability of dispersion of incident light
whereas the imaginary part ε2(ω) is a measure of energy (light) absorption of the material. The
graphical representation of the real part of the dielectric function ε1(ω) is shown in Fig. 8(a). The
static dielectric constant ε1(0) was noted 2.11, 2.57, 2.62, 2.76, and 2.83 for Cs2Ge(1-x)PtxCl6 with
x=0, 0.25, 0.50, 0.75, and 1.00 respectively. This can be noted that the values of ε1(0) have an
inverse relation with band gaps which is justified by Penn’s model as given by equation (4).

ħω
∈ (0) ≈∈1 (0) ≈ 1 + ( )2 (4)
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Fig. 8: Illustration of dielectric function (a) real parts, (b) imaginary parts, (c) absorption
coefficients, and (d) refractive indices for Cs2Ge(1-x)PtxCl6 with x=0, 0.25, 0.50, 0.75,1.00.

The imaginary part of the dielectric function ε2(ω) is shown in Fig. 8(b). It is clear that the
absorption edges move towards lower energies with the increasing percentage of Pt doping. The
prominent peaks occur at 3.40eV, 4.11eV, and 5.30eV and it can also be noted that the height of
the peaks increases with increasing Pt percentage.
The absorption coefficient calculated from equation (5) [70, 71] depicts the capability of incident
light absorption. It is evident from Fig. 8(c) that there are peaks in the visible region highlighted
in the figure that tells us the applicability of the materials in solar cells [72]. The prominent
peaks occur at 3.46eV, 4.12eV, and 5.52eV.
1⁄
⁄ 1 2
√2ω[{∈21 (ω) +∈22 (ω)} 2 −∈1 (ω)]
α(ω) = (5)
c

The refractive index is plotted in Fig. 8(d) calculated from equation (6) [70-72]. The recorded
values of static refractive indices are 1.45, 1.60, 1.61, 1.66, and 1.68 respectively for Cs2Ge(1-
x)PtxCl6 with x=0, 0.25, 0.50, 0.75,and 1. It can be noted that the relation 𝑛1 2 (0) ≈∈1 (0) is also
validated here [73].

1⁄
⁄ 1 2

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[{∈21 (ω) +∈22 (ω)} 2 +∈1 (ω)]
n(ω) = (6)
√2

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The optical conductivity, extinction coefficient, reflectivity, and electron loss function are

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represented graphically in Fig. 9 (a-d). The optical conductivity is calculated using equation (7)
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[74]
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α(ω)n(ω)c
σ(ω) = (7)
4π
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The major peaks of optical conductivities reside at 3.41, 4.08, and 5.31eV. It can be concluded
that there are also peaks of the significant values i.e. ~1015 sec-1 in the visible region having
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elevated peak maxima with increasing Pt-percentage so the charge carriers can play an active
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role in the visible region.

Similarly, the extinction coefficients obtained from equation (8), also known as the imaginary
part of refractive indices are shown in Fig.9 (b). Its visible peaks reside on 4.02eV, 6.01eV, and
7.62eV.

1⁄
1 ⁄ 2
[{∈21 (ω) +∈22 (ω)} 2 −∈1 (ω)]
K(ω) = (8)
√2

Reflectivity and electron loss function calculated from equations (9 and 10) are important to
measure the loss of incident light from reflection and other unwanted processes while passing
through the materials. Percentage reflectivity varies from 0.3-10% in the visible energy region as
shown in Fig. 9(c). Electron loss functions, shown in Fig. 9(d) have majority peaks far from the
visible region i.e. at 4.25eV and 6.38eV.
 (n−1)2 +K2
R(ω) = (9)
(n+1)2 +K2

∈2 (ω)
L(ω) = (10)
∈21 (ω) +∈22 (ω)

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Fig. 9 :Representation of (a) optical conductivity, (b) extinction coefficient, (c) reflectivity, and
(d) electron loss function for Cs2Ge(1-x)PtxCl6 with x=0, 0.25, 0.50, 0.75,and 1.

3.4 Thermoelectric Properties:

The efficiency of conversion of thermal to electrical energy can be assessed by a dimensionless

parameter known as the figure of merit (ZT) [75] that can be computed using equation (11).
S2 σT
ZT = (11)
к

Where S is the Seebeck coefficient, 𝜎 is the electrical conductivity and к is thermal conductivity.
A material with ZT close to or greater than unity is classified as efficient thermoelectric material.
This is possible only if the material has a large Seebeck coefficient along with a large electrical-
to-thermal conductivity ratio. A larger effective mass and smaller carrier concentration are
necessary for large Seebeck coefficients whereas the case is contrariwise for electrical
conductivity i.e. lower effective mass and larger carrier concentration are necessary for large
electrical conductivity [76-79]. Moreover, there is a direct relationship between 𝜎 and the
electronic part of thermal conductivity (кe) i.e. 𝜎∝кe according to Wiedemann-Franz law [80] so,
it is very interesting to explore such a material having a large Seebeck coefficient along with
large electrical conductivity and small thermal conductivity. Small band gap semiconductors
having sharp DOS peaks near the Fermi level are found to have fascinating thermoelectric

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properties because of the large Seebeck coefficient coupled with a large 𝜎/ к ratio.

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Herein, we investigated electrical conductivity, the electronic part of thermal conductivity, the

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Seebeck coefficient, and the Power factor w.r.t. the temperature as shown in Fig. 10 (a-d) for P-
type charge carriers. Electrical conductivity is constituted by the flow of current in response to
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the temperature gradient. The classical Drude model narrates that the relation for electrical
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𝑛𝑒 2 𝜏
conductivity at a particular temperature is 𝜎 = where n represents the charge density, e is
𝑚∗
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the charge of the electron or hole, 𝜏 the relaxation time and 𝑚∗ the effective mass [81]. The
relaxation time is considered constant (𝜏 ≈ 10−14 𝑠) under constant relaxation time
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approximation which is very successful for better approximation of various thermoelectric

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calculations [82, 83]. The 𝑚∗ can be obtained from the curvature of electronic band structures
[84]. We have computed 𝜎 versus T in a range of 0-800K that can be expressed mathematically
from equation (12) [85].

1 − ∂fo (T,μ,∈)
σ(T, μ) = ∫ σαβ (∈) [ ]∂ ∈ (12)
Ω ∂∈

Here the tensor of transport energy distribution is represented by 𝜎𝛼𝛽 (∈), the unit cell volume by
Ω, the chemical potential by 𝜇 that is equal to Fermi energy at absolute zero. The electrical
conductivity shows an increasing trend with temperature as shown in Fig. 10(a). It can be further
noted that Cs2Ge(1-x)PtxCl6 with x=0 has the highest value of 6.62×1018 (Ωms)-1 and furthermore,
the maxima of electrical conductivities decreases with increasing level of Pt-doping. The
maximum values are 2.35×1018 (Ωms)-1,0.87×1018 (Ωms)-1, 0.03×1018 (Ωms)-1, and 0.02×1018
(Ωms)-1 for x=0.25, 0.50, 0.75, and 1 respectively.
Thermal conductivity is contributed by electrons and phonons of the crystal known as the
electronic part (кe) and phononic part (кph) respectively. The materials having lower thermal
conductivity, especially with ultra-thin кph are very desirous for thermoelectric applications. The
major contribution in thermal conductivity comes from the electronic transport at high
1
temperatures since lattice contribution decreases with temperature i.e. к𝑝ℎ ∝ [86, 87].
𝑇

Therefore, it can be extracted from the above-mentioned literature that we can ignore the lattice
part of thermal conductivity at elevated temperatures. This is the reason that we adopted
BoltzTraP calculations which rely only on the electronic contribution of thermal conductivity.
Presently the trends of кe are similar to that of 𝜎 as shown in Fig. 10(b) for all studied

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compounds. This is in accordance with Wiedemann-Franz law [80]. The maximum values of кe

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are 2.51×1014 W/mKs, 2.79×1014W/mKs, 0.69×1014 W/mKs, 0.05×1014 W/mKs and 0.04×1014
W/mKs for x=0, 0.25, 0.50, 0.75,and 1 level of Pt-doping in Cs2Ge(1-x)PtxCl6.

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Fig. 10: Representations of temperature-dependent thermoelectric parameters (a) Electrical

conductivity (b) Electronic part of thermal conductivity (c) Seebeck coefficient, and (d) Power
factor for P-type charge carriers.
Thermopower alternatively known as the Seebeck coefficient is a proportionality constant of the
direct relationship between temperature gradient and the voltage difference across the contact
between two dissimilar materials.

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Fig. 11: Representations of temperature-dependent thermoelectric parameters (a) Electrical

conductivity (b) Electronic part of thermal conductivity (c) Seebeck coefficient, and (d) Power
factor for N-type charge carriers.

We can categorize a semiconductor to be N-type or P-type depending on the sign of

thermopower. The negative values of S depict the N-type and positive values portray the P-type
semiconductors. Mathematically, it is expressed by equation (13) [85].

1 − ∂fo (T,μ,∈)
S(T, μ) = (T,μ)
∫ σαβ (∈)(∈ −μ) [ ]∂ ∈ (13)
eTΩσαβ ∂∈

Seebeck coefficients have decreasing trend with temperature unlike electrical and thermal
conductivity as shown in Fig.10 (c). This dissimilar behavior between S and 𝜎 is justified by
literature [88-90]. The largest values of S are 1139 µV/K, 2789 µV/K, 2978 µV/K,3109 µV/K,
and 3296 µV/K for x=0, 0.25, 0.50, 0.75, and 1 level of Pt-doping in Cs2Ge(1-x)PtxCl6.

Power factor is the product of electrical conductivity and square of thermopower (P.F=𝜎𝑆 2 ).
There is a dissimilar relation between 𝜎 and S i.e. former has an increasing trend (In
semiconductors flow of charges increases with temperature unlike metals) and later has
decreasing trend with temperature (Increased flow of charges decreases thermal electromotive
force hence the Seebeck coefficient). Therefore, the P.F have neither maximum values at
maxima of S nor at maxima of 𝜎. Power factors have an increasing trend with temperature as
shown in Fig.10 (d). The highest P.F values are 2.70×1011 W/msK2,3.11×1011 W/msK2,0.79×1011

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W/msK2,0.06×1011 W/msK2,and 0.05×1011 W/msK2 for x=0, 0.25, 0.50, 0.75,1.00 level of Pt-

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doping in Cs2Ge(1-x)PtxCl6.

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Fig. 12: Illustration of Electrical conductivity as function of carrier concentration for Cs2Ge(1-
x)PtxCl6 (a) x=0.00 (b) x=0.25 (c) x=0.50, (d) x=0.75, and (e) x=1.00 at 200K, 400K, and 600K.
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Fig. 13: Seebeck coefficient as function of carrier concentration for Cs2Ge(1-x)PtxCl6 (a) x=0.00
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(b) x=0.25 (c) x=0.50, (d) x=0.75, and (e) x=1.00 at 200K, 400K, and 600K.
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Likewise, the Fig. 11(a-d) represents the behavior of N-type charge carriers for electrical
conductivity, the electronic part of thermal conductivity, the Seebeck coefficient, and the Power
factor w.r.t. the temperature respectively.

To have a further insight into the thermoelectric aspects, we also represented various key
thermoelectric parameters such as electrical conductivity and Seebeck coefficient as function of
carrier concentration in Figs. 12-13 at 200K, 400K, and 600K. It further supports that the
presence of both positive and negative charge carriers (holes and electrons), as it is clear from
the existence of positive and negative peaks of Seebeck effect [91-94] , the studied compounds
are quite reasonable for thermoelectric applications.

As mentioned at the start of this section, the thermoelectric efficiency of the figure of merit ZT
(given by equation 11) is the most important parameter to scrutinize a material for thermoelectric
device applications. A material having the value of ZT≥1 is considered appropriate for
thermoelectric devices. The ZT has a decreasing trend for all cases under study as can be seen
from Fig. 11. The recorded highest values vary from 0.98 to 1.00 with increasing levels of Pt-
doping. It can be noted that the increasing percentage of Pt clearly increases the overall ZT
values throughout the temperature range of 0-800K. The ZT values close to unity suggest that
these materials are very suitable for thermoelectric device applications.

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Fig. 14: Thermoelectric figure of merit versus temperature for Cs2Ge(1-x)PtxCl6 with x=0, 0.25,
0.50, 0.75, and 1.00.

Conclusion

In the current research, the structural, electronic, optical, and thermoelectric properties of
vacancy-ordered perovskites Cs2Ge(1-x)PtxCl6 with x=0, 0.25, 0.50, 0.75, and 1.00 are
investigated in detail. The structural stability of the compounds is assessed from Goldschmidt’s
tolerance (τt) and octahedral factors (μo) which lie in the stable perovskite structure range i.e. the
estimated values of τt are 1.04, 1.04, 1.03, 1.02, and 1.01 whereas the values of μo are 0.30, 0.31,
0.32, 0.33, and 0.34 for Cs2Ge(1-x)PtxCl6 with x=0, 0.25, 0.50, 0.75, and 1.00 respectively. The
lattice parameters fairly agree with the existing literature for Cs2Ge(1-x)PtxCl6 with x=0, and 1.00,
however, we have reported x= 0.25, 0.50, and 0.75 levels of Pt substitution for the first time. It is
observed that the lattice constants decrease with the increasing percentage of Pt. All the
compounds show direct band gaps with values 3.02eV, 2.98eV, 2.83eV, 2.62eV, and 2.50eV
with increasing Pt percentage from 0 to 100%. The decreasing trend in the band gap suggests
that the doping strategy is very effective in band gap tuning. It is interesting to note that the
absorption coefficients, optical conductivity, and refractive indices values increase with
increasing Pt percentage. Moreover, the thermoelectric parameters also increase with increasing
Pt percentage i.e. the Seebeck coefficients (1139 µV/K, to 3296 µV/K ) and figure of merits

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(0.98 to 1) for x=0-1 level of Pt-doping in Cs2Ge(1-x)PtxCl6. These promising trends suggest that
Pt-doping can be an excellent technique for better performance of solar cells and thermoelectric

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generators.

Acknowledgment:
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The authors would like to acknowledge the Researcher’s Supporting Project (RSP2023R71),
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King Saud University, Riyadh, Saudi Arabia for their support in this work.
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Data availability
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Data will be made available on request.

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Highlights
• New energy harvesting mechanisms as alternatives for traditional energy sources.
• Optoelectronics and thermoelectricity have gained much attention.
• The future of Perovskite thermoelectric generators.
• High absorption coefficient bismuth based double perovskite with reasonable band gaps.
• High figure of merit promising for thermoelectric applications.

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Declaration of interests

☑The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

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